Article
Biochemistry & Molecular Biology
Ervin Kovacs, Bence Balterer, Nguyen Anh Duc, Gyorgyi Szarka, Michael C. Owen, Attila Domjan, Bela Ivan
Summary: A large number of organic solvents contaminate the environment on a daily basis worldwide. This study demonstrates that benzotrifluoride can be used as a suitable solvent for olefin metathesis reactions, providing high yields and similar or even higher reaction rates compared to dichloromethane.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Multidisciplinary
Antonio Rizzo, Eunsong Jung, Hojoon Song, Yunhyeong Cho, Gregory I. Peterson, Tae-Lim Choi
Summary: Cascade polymerization of unique polycyclic enyne monomers was explored, with modifications to monomer structure parameters allowing control over polymerization performance and efficiency. By analyzing degradation products under mild acidic conditions, the cascade efficiency could be calculated, leading to controlled living cascade polymerizations of multiple monomers with high efficiency.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Samantha Brooks, Georgina Charlton, Aurelien Letort, Joelle Prunet, Goetz Bucher
Summary: Density-functional and semiempirical calculations on intermediates in ring-closing metathesis reactions in the synthesis of Taxol derivatives show excellent agreement with previous experimental results. The role of steric overloading in determining the outcome is highlighted, with rigidity of the Taxol skeleton playing a key role. Transition states in the final metathesis reaction stage are sensitive to steric effects. Predictions suggest preference for one diastereomer with a compact cyclic carbonate moiety, while a bulkier benzoate-protecting group results in prohibitive activation barriers. The orientation of the pseudoaxial methyl group on the cyclohexene ring likely determines the cascade formation pathway.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Samuel J. Kempel, Ting-Wei Hsu, Jake L. Nicholson, Quentin Michaudel
Summary: The stereochemistry of repeating alkenes in polymers has a significant impact on the thermal and mechanical properties of soft materials. However, there are limited methods to precisely control this parameter. In this study, a cis-selective acyclic diene metathesis (ADMET) polymerization was successfully developed using a highly stereoselective cyclometalated Ru catalyst, allowing for the synthesis of polymers with high cis contents up to 99%. The impact of cis geometry on the properties of polyalkenamers was investigated, demonstrating that cis-selective ADMET is an efficient strategy to tune the properties of various polymers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Fatema Jagot, Songeziwe Ntsimango, Kennedy J. Ngwira, Manuel A. Fernandes, Charles B. de Koning
Summary: This article describes the key steps in the synthesis of derivatives of angucycline, tetrangulol, including the catalyzed SuzukiMiyaura cross-coupling reaction, iron-catalyzed ring-closing carbonyl-olefin metathesis reaction, and late-stage oxidation reaction. The chlorinated compounds were obtained as final products.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Polymer Science
Mohammad Yasir, Andreas F. M. Kilbinger
Summary: Norbornene and cyclohexene show different polymerization behaviors using Grubbs' catalysts due to their varying ring strain energy levels; a sequence-selective cascade polymerization of a monomer containing both rings resulted in polymers with moderate molecular weight dispersities and good control over molecular weight.
Review
Chemistry, Multidisciplinary
Shrikant G. Pharande
Summary: Isocyanide-based multicomponent reactions (IMCR) and ruthenium-catalyzed ring-closing olefin metathesis (RCM) are powerful tools in organic synthesis, and their combination offers an efficient approach for the synthesis of complex cyclic olefins.
Article
Chemistry, Multidisciplinary
Nils Ansmann, Thaddaus Thorwart, Lutz Greb
Summary: The Lewis superacid bis(perchlorocatecholato)silane catalyzes C-O bond metathesis of alkyl ethers with high efficiency, enabling chemoselective ring contractions of macrocyclic crown ethers and unprecedented ring-closing metathesis of polyethylene glycols for polymer-selective degradation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Biochemistry & Molecular Biology
Anna Brodzka, Dominik Koszelewski, Ryszard Ostaszewski
Summary: The goal of diversity-oriented synthesis is to achieve structural diversity of compounds, but issues with low efficiency and multiple purification steps in kinetic resolution exist. A new concept has been proposed to simultaneously form two skeletally and enantiomerically diverse platform molecules in a one-pot protocol to overcome these limitations.
Article
Chemistry, Organic
Vachiraporn Ajavakom, Potchanee Pandokrak, Sofia S. Salim, Gamal A. I. Moustafa, Richard K. Bellingham, Joseph T. Hill-Cousins, Anawat Ajavakom, Richard C. D. Brown
Summary: A ring-closing metathesis (RCM) reaction of monobrominated dienes using Grubbs II catalyst was reported, giving moderate to good yields (40-80%) of seven-membered bromoolefins. Attempts to form five-, six-, or eight-membered bromoolefins through RCM were unsuccessful, except for one example that resulted in the formation of a bromomethyl-substituted cyclohexene as a byproduct. The selected bromoolefin RCM products showed utility in Suzuki-Miyaura reactions. Vinylic halide exchange (Br -> Cl) was observed as a side reaction under RCM conditions.
Review
Chemistry, Organic
Waqar Ahmed, Vikrant Jayant, Shakeel Alvi, Nadeem Ahmed, Azeem Ahmed, Rashid Ali
Summary: The synthesis of natural products has always been a top priority for synthetic chemists worldwide. Various synthetic methodologies have been used to extract, elucidate, synthesize, and document a wide range of natural products. The synthesis of complex natural products often presents challenges that can be overcome through modification or development of new synthetic methods. Metathesis tactics, discovered unexpectedly in the 1950s and awarded the Nobel Prize in 2005, have greatly influenced and changed the landscape of total and formal synthesis. This review article provides a comprehensive detail of metathetic tools used in the synthesis of natural products from 2017 to 2019.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Adrian Sytniczuk, Mariusz Milewski, Michal Dabrowski, Karol Grela, Anna Kajetanowicz
Summary: A set of macrocyclic unsaturated musk compounds were obtained through a high-concentration RCM process, achieved by forming oligomers and then undergoing backbiting metathesis reaction. The process exhibited high selectivity and yielded pure macrocyclic musk products. The reaction conditions were user-friendly and environmentally friendly, using commercially available catalyst and bio-sourced oleic acid substrates.
Article
Polymer Science
Arielle Mann, Marcus Weck
Summary: This contribution describes the synthesis of a novel unsymmetrical substituted tetraalkoxy[2.2]paracyclophane-1,9-diene and its polymerization to produce copolymers with alternating cis,trans-poly(p-phenylenevinylene)s. The synthesized polymers exhibit unique optical properties.
Article
Chemistry, Multidisciplinary
Dmitry S. Belov, Gabriela Tejeda, Charlene Tsay, Konstantin V. Bukhryakov
Summary: Vanadium-based catalysts have been demonstrated to catalyze ring-closing olefin metathesis reactions by well-defined V chloride alkylidene phosphine complexes, exhibiting good functional group tolerance. The properties of the imido group and phosphine were found to play a crucial role in the stability of active intermediates.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Andrea Ojeda-Porras, Remi Aouzal, Claire Wilson, Joelle Prunet
Summary: Two synthetic routes for the ABC tricycle of Taxol are presented, both involving a relay ring-closing metathesis reaction to form the central B ring. In the first approach, the extender arm is positioned on the A ring, while the C ring bears the relay tether in the second route. Despite the efficient synthesis of metathesis precursors with diverse extender arms, the crucial metathesis reactions failed to yield the target compounds in all cases.
Article
Chemistry, Multidisciplinary
Sofie M. P. Vanden Broeck, David J. Nelson, Alba Collado, Laura Falivene, Luigi Cavallo, David B. Cordes, Alexandra M. Z. Slawin, Kristof Van Hecke, Fady Nahra, Catherine S. J. Cazin, Steven P. Nolan
Summary: Readily prepared and bench-stable [Au(CF3)(NHC)] compounds were synthesized using new methods, and the mechanism of their formation was investigated. A straightforward strategy for the selective cleavage of a single carbon/fluorine bond from [Au(CF3)(NHC)] complexes was attempted, leading to the unprecedented spectroscopic observation of a gold(I)-NHC difluorocarbene species.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Applied
Vainius Skukauskas, Elliot L. B. Johnson Humphrey, Iain Hitchcock, Andrew York, Joseph Kelleher, Emma K. Gibson, David J. Nelson, Ian P. Silverwood
Summary: The article introduces the method of using neutron probes to observe the progress of catalytic reactions and the recent progress and possibilities in realistic applications.
TOPICS IN CATALYSIS
(2021)
Review
Chemistry, Multidisciplinary
Alba Collado, David J. Nelson, Steven P. Nolan
Summary: This review examines the use of phosphine and N-heterocyclic carbene complexes of gold(I) as (pre)catalysts in organic synthesis, categorizing them based on ligand structure and focusing on studies that offer quantitative comparisons with existing systems.
Article
Chemistry, Multidisciplinary
Joseph A. Zurakowski, Brady J. H. Austen, Maeve C. Dufour, Denis M. Spasyuk, David J. Nelson, Marcus W. Drover
Summary: The study demonstrates the importance of thoughtful ligand design in the intermolecular activation of iodobenzene in catalytic reactions. A specific nickel complex has shown excellent reactivity in this reaction. Furthermore, the secondary coordination sphere has been shown to have a significant impact on the formation of reaction products.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
Megan E. Greaves, Thomas O. Ronson, Feliu Maseras, David J. Nelson
Summary: The effects of ligand identity on the reaction rates of nickel-catalyzed alkyl halide reactions have been studied, showing that bulky and electron-donating ligands decrease reaction rates. The halide abstraction step may not always be irreversible, and certain ligands can lead to the formation of stable [Ni(dppf)(L)(2)] species. Additionally, the addition of free ligands significantly improves the yields of Kumada cross-coupling reactions.
Article
Chemistry, Multidisciplinary
Mitchell J. Demchuk, Joseph A. Zurakowski, Brady J. H. Austen, David J. Nelson, Marcus W. Drover
Summary: Transmetalation is a key method for constructing element-element bonds. Reactive [Ni-II(Ar)(I)(diphosphine)] compounds with arylgold(I) transmetalating agents may lead to aryl-for-iodide and unexpected aryl-for-aryl transmetalation, possibly complicating catalytic cross-coupling reactions.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Marina Saab, David J. Nelson, Matthew C. Leech, Kevin Lam, Steven P. Nolan, Fady Nahra, Kristof Van Hecke
Summary: In this study, we investigated the reactions of chalcogenoureas derived from N-heterocyclic carbenes with halogens and observed a diverse range of reactivity and structures depending on the structure of the chalcogenourea and the identity of the halogen. Cyclic voltammetry revealed that selenoureas are more easily oxidized than the corresponding thioureas, and a correlation between the oxidation potential and the electronic properties of the NHC was found in some cases. Furthermore, the reaction of these chalcogenoureas with different halogenating reagents was investigated, and the obtained products were characterized using NMR spectroscopy and single-crystal X-ray diffraction.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Elliot L. B. Johnson Humphrey, Alan R. Kennedy, Stephen Sproules, David J. Nelson
Summary: The use of a sodium in sodium chloride dispersion was systematically evaluated for the synthesis of nickel(0) and nickel(I) complexes from readily-prepared nickel(II) precursors. A variety of complexes with phosphine and bipyridine-type ligands were successfully accessed, although some reactions produced mixtures of nickel(0) and nickel(I) with highly variable yields. Several new nickel(I) complexes were obtained and characterized using techniques including NMR spectroscopy, EPR spectroscopy, and single crystal X-ray diffraction analysis.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Engineering, Electrical & Electronic
Dominique Coquillat, Emma O'Connor, Etienne V. V. Brouillet, Yoann Meriguet, Cedric Bray, David J. J. Nelson, Karen Faulds, Jeremie Torres, Nina Dyakonova
Summary: This study investigates the low-frequency vibrational spectroscopy of chlorophyll species using terahertz time-domain spectroscopy and Fourier transform infrared spectroscopy. The terahertz spectra of Chl-Mg-Na show clear features dominated by intermolecular interactions. The refractive index and absorption coefficient of Chl-Mg-Na were determined, and the temperature dependence of vibrational modes was studied. Furthermore, terahertz spectroscopy was used to analyze an ornamental plant, showing potential applications in agronomy.
JOURNAL OF INFRARED MILLIMETER AND TERAHERTZ WAVES
(2023)
Article
Chemistry, Physical
Nikolaos V. Tzouras, Leandros P. Zorba, Entzy Kaplanai, Nikolaos Tsoureas, David J. Nelson, Steven P. Nolan, Georgios C. Vougioukalakis
Summary: Despite the usefulness of gold catalysis in organic synthesis, it often requires activators and/or additives to generate cationic forms of gold catalysts. In this study, hexafluoroisopropanol (HFIP) is found to be a simple tool for gold-catalyzed cycloisomerizations, eliminating the need for external activators. HFIP acts as both a solvent and an activator through dynamic activation of the Au-Cl bond via hydrogen bonding. This unique mode of catalysis enables efficient and scalable cyclization reactions without the use of complex ligand/catalyst designs or activators.
Article
Chemistry, Multidisciplinary
Marissa L. Clapson, David J. Nelson, Marcus W. Drover
Summary: This report explores the coordination chemistry of monodentate phosphine-ligated nickel compounds and investigates the reactivity of allyl- and vinyl-substituted diphenylphosphine with [Ni(COD)(2)]. The reactions lead to intermolecularly tethered three-coordinate dinickelacycles through adjacent {Ni}-olefin interactions. The ring conformation of these cycles has been studied experimentally and theoretically. The presence of an allyl vs vinyl group is found to affect the reaction outcome, causing challenges in obtaining pure products.
ACS ORGANIC & INORGANIC AU
(2023)
Article
Chemistry, Multidisciplinary
Alasdair K. Cooper, Megan E. Greaves, William Donohoe, Paul M. Burton, Thomas O. Ronson, Alan R. Kennedy, David J. Nelson
Summary: A nickel/dppf catalyst system successfully achieved Suzuki-Miyaura cross-coupling reactions of certain chloropyridines and chloroquinolines but not others, due to differences in the reaction mechanism. Chloropyridines rapidly undergo oxidative addition to the catalyst, while alpha-halo-N-heterocycles form catalytically inactive dimeric nickel species.
Article
Chemistry, Physical
Daria S. Timofeeva, David M. Lindsay, William J. Kerr, David J. Nelson
Summary: In this study, the relationship between reaction rate and reaction selectivity in iridium-catalysed hydrogen isotope exchange reactions directed by Lewis basic functional groups was qualitatively examined. The findings show that selectivity and rate are not correlated, and different types of behaviors emerge in competition experiments, which can be predicted from an established selectivity scale.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Review
Chemistry, Physical
Megan E. Greaves, Elliot L. B. Johnson Humphrey, David J. Nelson
Summary: The review focuses on the reactions of nickel(0) complexes with organohalides, categorized based on the type of ligand present on nickel. The preferred reaction mechanism is influenced by a delicate balance of ligand and substrate structure, with small changes potentially leading to significant behavioral differences. This will impact the advancement of catalytic reactions using organohalide substrates and may affect ligand selection and the scope and limitations of the reactions.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Article
Electrochemistry
Shanthi Pandian, Krishnan S. Hariharan, Shashishekara P. Adiga, Subramanya Mayya Kolake
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
(2020)
Correction
Chemistry, Physical
Chen Luo, Yan Shao, Hua Yu, Hong-zhi Ma, Yu-hao Zhang, Long Gu, Bo Yin, Ming-bo Yang
CHEMICAL PHYSICS LETTERS
(2024)
Article
Chemistry, Physical
Stefano Borocci, Armando Camerlingo, Felice Grandinetti, Maria Rutigliano, Nico Sanna
Summary: The complexes of He, Ne, Ar, Kr, and Xe with B3N3H6 were investigated using MP2, CCSD(T), and SAPT ab initio methods. The complexes can be described as mono-, di-, and tri-coordinated to the N atoms, with stability following the order N-mono < N-di < N-tri. The interactions are dominated by dispersion and the binding energies are within the range of 1 or 2 kcal mol(-1). The results were compared with a recent DFT study on larger BN sheets complexes [Phys. Chem. Chem. Phys. 24 (2022) 2554-2566.].
CHEMICAL PHYSICS LETTERS
(2024)
Article
Chemistry, Physical
V. Nagarajan, R. Bhuvaneswari, R. Chandiramouli
Summary: In this study, stable phosphoborane was used as a sensor to detect isobutane and n-propane in Liquefied Petroleum Gas (LPG). Phosphoborane demonstrated structural stability and semiconducting nature, and exhibited promising adsorption properties for the LPG molecules.
CHEMICAL PHYSICS LETTERS
(2024)
Article
Chemistry, Physical
Xiaoxi Xu, Zijiang Yang, Bayaer Buren, Maodu Chen
Summary: In this study, the time-dependent wave packet method was used to investigate the reaction channels and mechanisms of Ca+ + HD. The results show that the CaH+ + D reaction channel plays a primary role, which is consistent with experimental results. Complex forming and direct-abstraction reaction mechanisms exist in this reaction process.
CHEMICAL PHYSICS LETTERS
(2024)
Article
Chemistry, Physical
Keshab Pandey, Hae Kyung Jeong
Summary: A free-standing silicon-carbon nanofiber composite film was synthesized and investigated for supercapacitor applications. It exhibited high specific capacitance, energy density, and power density. After 5000 cycles, the film showed excellent specific capacitance retention and Coulombic efficiency.
CHEMICAL PHYSICS LETTERS
(2024)
Article
Chemistry, Physical
Xinyu Zhang, Haosong Li, Xiaoyu Cao, Jing Gao, Yong Wei, Jianzhuo Zhu
Summary: The evaporation behavior of nanosized water aggregations on two-dimensional electroneutral solid surfaces with different surface polar unit densities was investigated. The results showed that the evaporation rate changes non-monotonically with the surface polar unit density, and the minimum evaporation rate is obtained when the surface has a modest surface polar unit ratio of 66.7%.
CHEMICAL PHYSICS LETTERS
(2024)
Article
Chemistry, Physical
Yanyan Xu, Rui Dai, Xiaojie Wang, Zhijun Qiao, Haowei Wen, Dianbo Ruan, Yuzuo Wang
Summary: This article presents an innovative solvothermal sodium insertion method for synthesizing Triphylite-NaFePO4, which demonstrates optimal electrochemical performance in sodium-ion batteries.
CHEMICAL PHYSICS LETTERS
(2024)
Article
Chemistry, Physical
Meiyi Jiang, Kun Yang, Yancheng Liu, Li Yao
Summary: The geometric structure and electronic properties of transition metal M (M = Cu, Fe, Mn)-TiO2 (101) surface adsorbed by NO2 and N2O were calculated by density functional theory (DFT) and DFT + U theory. The results showed that the adsorption of NO2 and N2O on Mn and Fe atoms is more stable, and a large number of active electrons are formed around these atoms, facilitating the catalytic reactions.
CHEMICAL PHYSICS LETTERS
(2024)
Article
Chemistry, Physical
Sergey A. Vyrko, Yulia G. Polynskaya, Nikita A. Matsokin, Andrey M. Popov, Andrey A. Knizhnik, Nikolai A. Poklonski, Yurii E. Lozovik
Summary: In this study, carbon nanobracelets, which are cyclic molecules composed of alternating polycyclic regions and double carbon chains, were investigated using spin-polarized density functional theory. The results show that carbon nanobracelets with odd number of monomers exhibit distinct electronic energy levels, band gaps, and carbon chain deformation compared to those with even number of monomers.
CHEMICAL PHYSICS LETTERS
(2024)
Article
Chemistry, Physical
Chanchan Wang, Quan Yang, Yanzhi Ding, Xiaoyong Lu, Dong Tian
Summary: It has been found that the introduction of buffer layers improves the electrical performance of solid oxide fuel cells (SSOFCs). In this study, varying ratios of Gd-doped CeO2 were used as buffer layers in YSZ-based SSOFCs. The results demonstrate that the performance of SSOFCs is enhanced when a buffer layer is added, with the highest performance achieved using Ce0.8Gd0.2O2-delta (GDC20) as the buffer layer. This suggests that the use of GDC series buffer layers is an attractive strategy to optimize performance loss due to electrolyte-electrode interactions.
CHEMICAL PHYSICS LETTERS
(2024)
Article
Chemistry, Physical
Wang Li, Yi-Fan Zhang, Jia-Bin Huang, Chang-Yang Wang, Feng Zhang, Jiu-Zhong Yang, Long Zhao
Summary: The gas-phase reaction of propargyl with vinylacetylene was investigated using synchrotron photoionization and molecular-beam mass spectrometry methodologies. The formation mechanisms of the resulting cyclic structures were examined using quantum computations. Two previously unidentified isomers were detected and identified for the first time.
CHEMICAL PHYSICS LETTERS
(2024)
Article
Chemistry, Physical
Avijit Pramanik, Sanchita Kundu, Olorunsola Praise Kolawole, Kaelin Gates, Paresh Chandra Ray
Summary: This study investigates the influence of aspect ratio and quantum confinement on the single-photon and two-photon absorption cross-section of perovskite CsPbI3 nanorods. Experimental data shows that CsPbI3 nanorods have an extremely high two-photon absorption cross-section, significantly surpassing organic chromophores and other CsPbBr3 nanocrystals. Moreover, adjusting the aspect ratio can significantly enhance the absorption ability. Additionally, the study also reveals a moderate quantum confinement effect on the single-photon and two-photon absorption cross-section of the nanorods.
CHEMICAL PHYSICS LETTERS
(2024)
Article
Chemistry, Physical
Hyon-Tae Pak, Jin-A Choe, Kyong-Sik Ju, Yong -Son Rim
Summary: Drug-loaded cellulose diacetate (CDA) membranes were prepared using different compositions of mixed solvent. The microstructure and performance of the membranes were investigated, and a method to predict drug release properties was proposed. The results showed that the composition of the mixed solvent significantly affected the overall performance of CDA membranes, and the release rates of drugs were related to Δdelta and the intrinsic viscosity of CDA.
CHEMICAL PHYSICS LETTERS
(2024)
Article
Chemistry, Physical
Gabriella E. Ravin, E. Curotto
Summary: We have developed a systematic approach to optimize the training set sizes for neural networks in fitting ab initio potential energy surfaces. Using this approach, we have constructed several spectroscopic quality potential energy surfaces for [Li(H2)n]+, n = 1 - 9. The ground state properties have been computed for all the systems and selected states.
CHEMICAL PHYSICS LETTERS
(2024)
Article
Chemistry, Physical
Guohua Xu, Lei Xu, Feng Zhang, Chunling Yu, Yu Song
Summary: NiS1.03@Ni7S6/carbon composite was successfully prepared using corn stalk as a carbon source via a simple adsorption-sulphurization process. The composite exhibited a specific capacitance of 1554.6 F/g at 1 A/g as a supercapacitor electrode, with a capacitance retention rate of 80.4% after 5000 cycles. Furthermore, the NiS1.03@Ni7S6/carbon//AC asymmetric supercapacitor showed a high energy density of 41.2 Wh kg-1 at a power density of 750 W kg-1, and excellent cycling stability with 86.8% capacitance retention after 10,000 cycles.
CHEMICAL PHYSICS LETTERS
(2024)
